Azo dyes containing sulfonic acid groups and oxdiazolyl radicals

ABSTRACT

Compounds which in the form of the free acids have the formula I ##STR1## where K is the radical of a coupling component, n is 1, 2 or 3, R 1  is hydrogen, chlorine, bromine or hydroxysulfonyl, R 2  is hydrogen, chlorine, bromine, nitro, methyl or trifluoromethyl and R 3  is hydrogen, alkyl of 1 to 8 carbon atoms (which may or may not be interrupted by oxygen and may be unsubstituted or substituted by hydroxyl, alkoxy of 1 to 8 carbon atoms, phenyl or phenoxy), benzyl, phenylethyl, cyclohexyl, phenyl (which may be unsubstituted or substituted by chlorine, bromine, nitro, methyl, ethyl, methoxy, ethoxy, phenoxy, dialkylamino, where alkyl is of 1 to 4 carbon atoms, or hydroxysulfonyl), naphthyl, pyridyl, thienyl or furyl. The compounds of the formula I may be used for dyeing nitrogen-containing fibers; the dyeings obtained are very fast and have brilliant hues.

The present invention relates to compounds which in the form of the free acids correspond to the formula I ##STR2## where K is the radical of a coupling component, n is 1, 2 or 3, R¹ is hydrogen, chlorine, bromine or hydroxysulfonyl, R² is hydrogen, chlorine, bromine, nitro, methyl or trifluoromethyl and R³ is hydrogen, alkyl of 1 to 8 carbon atoms (which may or may not be interrupted by oxygen and may be unsubstituted or substituted by hydroxyl, alkoxy of 1 to 8 carbon atoms, phenyl or phenoxy), benzyl, phenylethyl, cyclohexyl, phenyl (which may be unsubstituted or substituted by chlorine, bromine, nitro, methyl, ethyl, methoxy, ethoxy, phenoxy, dialkylamino, where alkyl is of 1 to 4 carbon atoms, or hydroxysulfonyl, naphthyl, pyridyl, thienyl or furyl.

The radicals K of the coupling components are in the main derived from the phenol, aniline, naphthol, naphthylamine, aminonaphthol, acetoacetarylide, pyrazolone, aminopyrazole, pyridone, diaminopyridine, triaminopyridine, diaminopyrimidine, triaminopyrimidine, barbituric acid, quinoline, isoquinoline or indole series.

Specific examples of coupling components are those of the formula ##STR3## where B¹ and B² independently of one another are hydrogen, alkyl of 1 to 4 carbon atoms, alkyl of 2 to 4 carbon atoms which is substituted by hydroxyl, cyano, alkoxy of 1 to 4 carbon atoms, alkanoyloxy of 1 to 4 carbon atoms or alkoxycarbonyl (where alkoxy is of 1 to 4 carbon atoms), alkyl of 4 to 9 carbon atoms which is interrupted by oxygen and substituted by hydroxyl, alkoxy of 1 to 4 carbon atoms, phenoxy or benzyloxy, cyclohexyl, benzyl, phenylethyl or phenyl, B³ is hydrogen, hydroxysulfonyl, chlorine, methyl or alkanoylamino of 1 to 4 carbon atoms, B⁴ is phenyl which may be unsubstituted or substituted by hydroxysulfonyl, chlorine, bromine, methyl, ethyl, methoxy or ethoxy, B⁵ is hydrogen, alkyl of 1 to 4 carbon atoms, cyclohexyl, benzyl or phenyl which may be unsubstituted or substituted by chlorine, bromine, methyl, ethyl or hydroxysulfonyl, B⁶ is hydroxyl or amino, B⁷ is hydrogen, methyl, carbamoyl or alkoxycarbonyl where alkoxy is of 1 to 4 carbon atoms), B⁸ is cyano or carbamoyl, B⁹ is hydrogen, hydroxyl or methyl, B¹⁰ is a radical B¹ or ##STR4## B¹¹ is a radical B¹ or ##STR5## B¹² is methyl or phenyl, B¹³ is hydrogen, methyl, β-cyanoethyl, β-hydroxyethyl, β-carboxyethyl or β-carbamoylethyl and p is 0, 1 or 2.

Specific examples of radicals B¹ and B², in addition to those already mentioned, are: CH₃, C₂ H₅, C₃ H₇, C₄ H₉, C₂ H₄ OH, CH₂ CHOHCH₃, CH₂ CHOHCH₂ Cl, CH₂ CH₂ CN, CH₂ CH₂ OCH₃, CH₂ CH₂ OC₂ H₅, CH₂ CH₂ OC₄ H₉, ##STR6## CH₂ CH₂ OCOCH₃, CH₂ CH₂ OCOC₂ H₅, CH₂ CH₂ COOCH₃, CH₂ CH₂ COOC₂ H₅, CH₂ CH₂ COOC₄ H₉, CH₂ CH₂ OCH₂ CH₂ OH, (CH₂)₃ OCH₂ CH₂ OH, (CH₂)₃ O(CH₂)₄ OH, (CH₂)₃ OC₂ H₄ OCH₃, (CH₂)₃ OC₂ H₄ OC₂ H₅, (CH₂)₃ OC₂ H₄ OC₄ H₉, (CH₂)₃ OC₂ H₄ OCH₂ C₆ H₅, (CH₂)₃ OC₂ H₄ OC₆ H₅, (CH₂)₃ O(C₂ H₄ O)₂ CH₃ and (CH₂)₃ O(C₂ H₄ O)₂ C₂ H₅.

Examples of preferred diazo components are: ##STR7##

Preferred coupling components have the formulae ##STR8##

On natural polyamides and synthetic nylons, the dyes of the formula I give yellow to red dyeings with very good lightfastness and wetfastness. The depth of color and the clear hue achievable with many dyes deserve particular mention. The dyes may be used in the form of their alkali metal salts (the alkali metal being Li, Na or K) or of their ammonium salts (where ammonium may be unsubstituted or substituted).

Dyes of particular industrial importance are those of the formula Ia ##STR9## where R⁴ is hydrogen, chlorine or hydroxysulfonyl, R⁵ is hydrogen, chlorine or trifluoromethyl, R⁶ is methyl, alkoxyethyl (where alkoxy is of 1 to 4 carbon atoms), phenoxyethyl, phenyl which may be unsubstituted or substituted by hydroxysulfonyl, or pyridyl, m is 1 or 2 and K¹ is a coupling component of the aniline, naphthol, naphthylamine, aminonaphthol, acetoacetarylide, pyrazolone, aminopyrazole, pyridone, diaminopyridine or indole series.

The dyes of the formula I may be manufactured by reacting a diazonium compound of an amine of the formula ##STR10## with a coupling component of the formula

    HK;

the n sulfonic acid groups may be present in the diazo component and/or in the coupling component.

In the Examples which follow, parts and percentages are by weight, unless stated otherwise.

EXAMPLE 1

A solution of 34 parts of the sodium salt of the formula (2) in 200 parts of water is added to a mixture of 300 parts of ice and 35 parts by volume of 10-molar hydrochloric acid. 30 parts by volume of a 23% strength aqueous sodium nitrite solution is run in under the surface of this mixture at 0°-5° C., stirring is continued for 3 hours at this temperature, and the excess nitrous acid is then destroyed in the conventional manner by adding amidosulfonic acid.

A solution of 25 parts of acetoacetic acid 2,4-dimethoxyanilide in 250 parts by volume of glacial acetic acid is run into the resulting diazotized mixture at 0°-5° C., after which 750 parts by volume of a 55% strength aqueous sodium acetate solution are run in. The dye is filtered off and washed with dilute sodium chloride solution; it is a yellow powder which gives a greenish yellow solution in hot water. On nylon or wool fabrics it gives greenish yellow dyeings with excellent lightfastness and wetfastness.

EXAMPLE 2

A solution of 19 parts of 1-phenyl-3-methyl-5-aminopyrazole in 20 parts of 10-molar hydrochloric acid and 500 parts of water is run slowly, at 0°-5° C., into the diazotized mixture obtained as described in Example 1, paragraph 1, after which 400 parts by volume of a 55% strength aqueous sodium acetate solution are run in. The dye obtained is filtered off and washed with dilute sodium chloride solution and then with a little water. After drying at 100° C., a yellow powder is obtained, which dyes nylon fibers in yellow hues having very good lightfastness and wetfastness.

EXAMPLE 3

A solution of 25 parts of 2,6-bis-(2-hydroxyethylamino)-3-cyano-4-methylpyridine in 15 parts by volume of concentrated hydrochloric acid and 500 parts of water is added gradually, at 0°-5° C., to the diazotized mixture prepared as described in Example 1, paragraph 1, and sufficient saturated sodium acetate solution is then added to give a pH of from 4 to 5. The dye is filtered off after completion of coupling, washed with a little water and dried at 100° C. An orange powder is obtained, which gives a golden yellow solution in hot water and dyes nylon textiles in yellowish orange hues which have very good lightfastness and wetfastness.

EXAMPLE 4

The diazotized mixture obtained as described in Example 1, paragraph 1, is added at 0°-5° C. to a solution of 32 parts of N-ethyl-N-benzyl-aniline-3'-sulfonic acid in 10 parts of 50% strength sodium hydroxide solution and 500 parts of water, 500 parts of ice and 20 parts of sodium carbonate also being added. The dye is precipitated from the resulting solution by adding 1,000 parts by volume of saturated sodium chloride solution and is filtered off, washed with dilute sodium chloride solution and dried. The yellowish brown powder obtained readily dissolves in water and gives orange dyeings, having very good lightfastness and wetfastness, on nylon filaments.

EXAMPLE 5

24 parts of the compound of the formula (1) are dissolved in 250 parts of glacial acetic acid and 50 parts of propionic acid. 32 g of 40% strength nitrosylsulfuric acid are added dropwise at from 0° to 5° C. and the mixture is then stirred for 2 hours at the same temperature. The excess nitrous acid is then destroyed in the conventional manner by adding urea.

The diazotized mixture obtained is added at 0°-5° C. to a mixture which has been obtained by dissolving 26 parts of 2-amino-8-hydroxynaphthalene-6-sulfonic acid in 300 parts of water containing 7.5 parts by volume of 50% strength sodium hydroxide solution, and then adding 60 parts by volume of 10% strength hydrochloric acid and 300 parts of ice to the solution.

Sufficient saturated sodium acetate solution is then slowly added dropwise to the coupling mixture until the pH has reached 2-3.

After completion of coupling, the mixture is neutralized with 50% strength sodium hydroxide solution to a pH of 6-8, and the dye is then filtered off, washed with water and dried. A dark red powder is obtained, which gives a red solution in hot water and dyes nylon fabrics in red hues having very good lightfastness and wetfastness.

EXAMPLE 6

24 parts of the compound of the formula (6) are stirred into 120 parts of water and 40 parts of concentrated hydrochloric acid at room temperature. The mixture is then made up to 500 parts by volume with water and ice. After adding 30 parts by volume of a 23% strength sodium nitrite solution of from 5° to 10° C., the mixture is stirred for 2 hours and excess nitrous acid is destroyed in the conventional manner.

The diazonium salt solution thus obtained is coupled with 26 parts of 2-amino-8-hydroxynaphthalene-6-sulfonic acid by the method described in Example 5, paragraph 2. The dye thus obtained gives red dyeings, having very good lightfastness and wetfastness, on nylon fabrics.

If the methods described in the preceding Examples are followed, starting from the components indicated in the Table, the corresponding dyes are obtained.

    __________________________________________________________________________     Diazo component                                                                 ##STR11##                                                                                                            Hue of a                                Ex-                                    dyeing                                  ample                                                                              R                       Coupling component                                                                        on nylon                                __________________________________________________________________________      7  CH.sub.3                                                                                                ##STR12## red                                      8  CH.sub.2CH.sub.2OCH.sub.3                                                                              "          "                                        9  CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.3                                                             "          "                                       10                                                                                  ##STR13##              "          "                                       11                                                                                  ##STR14##              "          "                                       12                                                                                  ##STR15##              "          "                                       13                                                                                  ##STR16##              "          "                                       14                                                                                  ##STR17##              "          "                                       15  CH.sub.2CH.sub.3        "          "                                       16                                                                                  ##STR18##              "          "                                       17                                                                                  ##STR19##              "          "                                       18                                                                                  ##STR20##              "          "                                       __________________________________________________________________________

    __________________________________________________________________________     Ex-                                                                            ample                                                                              Diazo component     Coupling component       Hue                           __________________________________________________________________________     19                                                                                  ##STR21##                                                                                          ##STR22##               red                           20                                                                                  ##STR23##          "                        red                           21                                                                                  ##STR24##          "                        red                           22  Formula (1)                                                                                         ##STR25##               yellow                        23  "                   "                        yellow                        24  "                                                                                                   ##STR26##               yellow                        25  "                   "                        yellow                        26  "                                                                                                   ##STR27##               yellow                        27  "                                                                                                   ##STR28##               orange                        28  "                                                                                                   ##STR29##               orange                        29  "                                                                                                   ##STR30##               yellow                        30  "                                                                                                   ##STR31##               yellow                        31  "                                                                                                   ##STR32##               yellowish orange              32  "                                                                                                   ##STR33##               yellow                        33  "                                                                                                   ##STR34##               yellow                        34  "                                                                                                   ##STR35##               yellowish red                 35  Formula (7)                                                                                         ##STR36##               yellow                        36  Formula (8)         "                        yellow                        37  Formula (6)         "                        yellow                        38  "                                                                                                   ##STR37##               yellow                        39  "                                                                                                   ##STR38##               "                             40  "                                                                                                   ##STR39##               yellowish orange              41  "                                                                                                   ##STR40##               orange                        42  "                                                                                                   ##STR41##               yellowish red                 43  Formula (2)                                                                                         ##STR42##               yellow                        44  "                                                                                                   ##STR43##               yellow                        45  "                                                                                                   ##STR44##               yellow                        46  "                                                                                                   ##STR45##               yellow                        47  "                                                                                                   ##STR46##               yellow                        48  "                                                                                                   ##STR47##               yellow                        49  "                                                                                                   ##STR48##               yellow                        50  "                                                                                                   ##STR49##               "                             51  "                                                                                                   ##STR50##               "                             52  "                                                                                                   ##STR51##               orange                        53  "                                                                                                   ##STR52##               red                           54  "                                                                                                   ##STR53##               yellowish orange              55  "                                                                                                   ##STR54##               yellow                        56  "                                                                                                   ##STR55##               yellow                        57  "                                                                                                   ##STR56##               yellow                        58  "                                                                                                   ##STR57##               yellow                        59  Formula (3)                                                                                         ##STR58##               yellow                        60  "                                                                                                   ##STR59##               yellow                        61  "                                                                                                   ##STR60##               yellow                        62  "                                                                                                   ##STR61##               yellow                        63  "                                                                                                   ##STR62##               yellow                        64  "                                                                                                   ##STR63##               yellow                        65  "                                                                                                   ##STR64##               orange                        66  "                                                                                                   ##STR65##               yellowish red                 67  "                                                                                                   ##STR66##               yellowish  orange             68  "                                                                                                   ##STR67##               yellowish  orange             69  "                                                                                                   ##STR68##               yellow                        70  "                                                                                                   ##STR69##               yellow                        71  "                                                                                                   ##STR70##               yellow                        72  "                                                                                                   ##STR71##               yellow                        73  "                                                                                                   ##STR72##               yellow                        74  "                                                                                                   ##STR73##               yellow                        75  "                                                                                                   ##STR74##               yellow                        76  "                                                                                                   ##STR75##               yellow                        77  "                                                                                                   ##STR76##               orange                        78  "                                                                                                   ##STR77##               yellowish   red               79  "                                                                                                   ##STR78##               yellowish  orange             80  "                                                                                                   ##STR79##               yellowish  orange             81  "                                                                                                   ##STR80##               yellow                        82  "                                                                                                   ##STR81##               yellow                        83  Formula (4)                                                                                         ##STR82##               yellow                        84  "                                                                                                   ##STR83##               yellow                        85  "                                                                                                   ##STR84##               yellow                        86  "                                                                                                   ##STR85##               yellow                        87  "                                                                          88  "                    ##STR86##               " -                                                    ##STR87##               yellow                        89  "                                                                                                   ##STR88##               yellowish orange              90  "                                                                                                   ##STR89##               yellowish orange              91                                                                                  ##STR90##                                                                                          ##STR91##               orange                        92  "                                                                                                   ##STR92##               red                           93  "                                                                                                   ##STR93##               yellow                        94                                                                                  ##STR94##                                                                                          ##STR95##               yellow                        95  "                                                                                                   ##STR96##               orange                        96                                                                                  ##STR97##                                                                                          ##STR98##               red                           97  "                                                                                                   ##STR99##               yellow                        98  "                                                                                                   ##STR100##              "                             99                                                                                  ##STR101##                                                                                         ##STR102##              orange                        100                                                                                 ##STR103##         "                        "                             101 "                                                                                                   ##STR104##              yellow                        102 "                                                                                                   ##STR105##              yellowish orange              103 "                                                                                                   ##STR106##              yellow                        104 Formula (5)                                                                                         ##STR107##              red                           105 "                                                                                                   ##STR108##              orange                        106 "                                                                                                   ##STR109##              "                             107 "                                                                                                   ##STR110##              yellowish red                 108 "                                                                                                   ##STR111##              yellowish orange              109 "                                                                                                   ##STR112##              yellowish orange              110 "                                                                                                   ##STR113##              yellowish orange              111                                                                                 ##STR114##                                                                                         ##STR115##              yellow                        112   "                                                                                                 ##STR116##              "                             113   "                                                                                                 ##STR117##              orange                        114 Formula 14                                                                                          ##STR118##              red                           115   "                                                                                                 ##STR119##              yellow                        116   "                                                                                                 ##STR120##              yellow                        117   "                                                                                                 ##STR121##              yellowish orange              118   "                                                                                                 ##STR122##              orange                        119   "                                                                                                 ##STR123##              yellowish red                 120                                                                                 ##STR124##                                                                                         ##STR125##              red                           121 "                                                                                                   ##STR126##              yellow                        122                                                                                 ##STR127##                                                                                         ##STR128##              orange                        123 "                                                                                                   ##STR129##              red                           124 "                                                                                                   ##STR130##              yellow                        125 "                                                                                                   ##STR131##              "                             126 "                                                                                                   ##STR132##              "                             127                                                                                 ##STR133##                                                                                         ##STR134##              yellow                        128                                                                                 ##STR135##                                                                                         ##STR136##              yellow                        129 "                                                                                                   ##STR137##              yellowish red                 130 Formula (2)                                                                                         ##STR138##              yellow                        131 "                                                                                                   ##STR139##              yellowish orange              132 "                                                                                                   ##STR140##              orange                        133 "                                                                                                   ##STR141##              yellowish red                 134 "                                                                                                   ##STR142##              yellow                        135 "                                                                                                   ##STR143##              orange                        136                                                                                 ##STR144##                                                                                         ##STR145##              red                           137 "                                                                                                   ##STR146##              yellow                        138 "                                                                                                   ##STR147##              yellowish red                 139 "                                                                                                   ##STR148##              yellow                        140                                                                                 ##STR149##                                                                                         ##STR150##              yellow                        141 "                                                                                                   ##STR151##              red                           142 "                                                                                                   ##STR152##              yellow                        143 "                                                                                                   ##STR153##              yellow                        144 "                                                                                                   ##STR154##              yellow                        145 "                                                                                                   ##STR155##              yellow                        146 "                                                                                                   ##STR156##              yellow                        147 "                                                                                                   ##STR157##              yellow                        148 "                                                                                                   ##STR158##              bluish                        __________________________________________________________________________                                                      red                      

    __________________________________________________________________________     Example                                                                             Dye                               Hue                                     __________________________________________________________________________     149                                                                                  ##STR159##                       golden yellow                           150                                                                                  ##STR160##                       reddish yellow                          151                                                                                  ##STR161##                       "                                       152                                                                                  ##STR162##                       orange                                  153                                                                                  ##STR163##                       bluish red                              154                                                                                  ##STR164##                       dull bluish red                         __________________________________________________________________________ 

We claim:
 1. An acid azo dye which in the form of the free acid has the formula ##STR165## where R¹ is hydrogen, chlorine or bromine,R² is hydrogen, chlorine, bromine, nitro, methyl or trifluoromethyl, R³ is hydrogen; C₁ to C₈ alkyl; C₁ to C₈ alkyl substituted by hydroxy, C₁ to C₈ alkoxy or phenoxy; C₂ to C₈ alkyl interrupted by oxygen and substituted by hydroxy or phenyl; benzyl; phenylethyl; cyclohexyl; phenyl; phenyl substituted by chlorine, bromine, nitro, methyl, ethyl, methoxy, ethoxy, phenoxy or di-C₁ to C₄ -alkylamino; naphthyl; pyridyl; thienyl; or furyl; n is 1, 2 or 3 and K is ##STR166## where B¹ and B² independently of one another are hydrogen; C₁ to C₄ alkyl; C₂ to C₄ alkyl substituted by hydroxy, cyano, C₁ to C₄ alkoxy, C₁ to C₄ alkanoyloxy or C₁ to C₄ alkoxycarbonyl; C₃ to C₉ alkyl interrupted by oxygen and substituted by hydroxy or phenyl; cyclohexyl; benzyl; phenylethyl or phenyl;B³ is hydrogen, chlorine, methyl, C₁ to C₄ alkanoylamino or hydroxysulfonyl, B⁴ is phenyl or phenyl substituted by chlorine, bromine, methyl, ethyl, methoxy or ethoxy, B⁵ is hydrogen, C₁ to C₄ alkyl, cyclohexyl, benzyl, phenyl or phenyl substituted by chlorine, bromine, methyl or ethyl, B⁶ is hydroxy or amino, B⁷ is hydrogen, methyl, carbamoyl or C₁ to C₄ alkoxycarbonyl, B⁸ is cyano or carbamoyl, B⁹ is hydrogen, hydroxy or methyl, B¹⁰ is B¹ or ##STR167## B¹¹ is B¹ or ##STR168## B¹² is methyl or phenyl, B¹³ is hydrogen, methyl, β-cyanoethyl, β-hydroxyethyl, β-carboxyethyl or β-carbamoylethyl and p is 0, 1 or 2 and the n hydroxysulfonyl groups are present in the radicals R³ or K or in the ring bearing the substituents R¹ and R².
 2. A dye according to the formula in claim 1, in which R¹ is hydrogen.
 3. A dye according to the formula in claim 1, in which R¹ is hydrogen and R² is hydrogen, chlorine, nitro or trifluoromethyl.
 4. A dye according to the formula in claim 1, in which R³ is C₁ to C₄ alkyl, C₁ - to C₄ alkyl substituted by C₁ to C₈ alkoxy, phenoxy, benzyloxy or phenylethoxy, phenyl or phenyl substituted by chlorine, methyl, methoxy or ethoxy.
 5. A dye according to the formula in claim 1, in whichK is ##STR169## B¹ to B¹¹ having the meanings given in claim
 1. 6. The dye according to claim 1 of the formula ##STR170##
 7. The dye according to claim 1 of the formula ##STR171##
 8. The dye according to claim 1 of the formula ##STR172##
 9. The dye according to claim 1 of the formula ##STR173##
 10. The dye according to claim 1 of the formula ##STR174## 